Crosslinked Polyvinylpyrrolidone Compositions

ABSTRACT

Low-dusting, granular compositions are provided that comprise at least 15% by weight crosslinked polyvinylpyrrolidone.

This application claims priority to provisional patent application No.61/119,463, which was filed on Dec. 3, 2008.

FIELD OF THE INVENTION

The invention relates to low-dusting, crosslinked polyvinylpyrrolidonecompositions, methods to produce them, and their uses, especially inbeverage treatment.

DESCRIPTION OF PRIOR ART

Crosslinked polyvinylpyrrolidone (PVPP), known by the generic chemicalname crospovidone in pharma applications, is a water-insoluble,water-swellable, hydrophilic polymer that finds application in multipleindustries. It is used in the beverage industries as a drink clarifierand stabilizer, where it binds polyphenols that may lead to astringentflavors and/or hazing (clouding). The complexations through hydrogenbonding and/or dipolar interactions also enable PVPP to serve as a dyescavenger for printing and laundry applications. Finally, due to itscompressibility and swelling capacity, crospovidone is widely used inpharmaceutical/nutritional products as a tablet disintegrant.

Commercial PVPP products is sold into commercial sale by a number ofmanufacturers/suppliers. Polyplasdone® and Polyclar® grades areavailable from International Specialty Products (Wayne, N.J.). Threegrades comprise the Polyplasdone® product line: INF-10, XL, and XL-10.Seven products comprise the Polyclar® product line: Polyclar® 10,Brewbrite™, Plus 730, Super R, Ultra K-100, V, and VT. The Polyclar®Brewbrite™ is a physical blend of PVPP and carrageenan that is effectiveas a wort clarifier and beer stabilizer. Polyclar® Plus 730 is a beerstabilizer and clarifier consisting of physically blended PVPP andsilica xerogel. It is described in U.S. Pat. No. 7,153,534 and isincorporated herein its entirety by reference.

Additionally, the following marketing brochures of InternationalSpecialty Products describe these PVPP products used in beverageapplications, and hereby are incorporated in their entirety byreference: “Functional drink, tea, and juice stabilizers, clarifiers andtexturizers,” “Polyclar® 10, Single-use PVPP beer stabilizer,”“Polyclar® Brewbrite™, Wort clarifier & beer stabilizer,” “Polyclar®Plus 730, Single-use balanced beer stabilizer,” “Polyclar® Plus,Prescription clarification and stabilization of beer,” “Polyclar® UltraK-100, Wine stabilizer & clarifier,” “Polyclar® for wine,” “Polyclar®for beer,” “Polyclar® stabilizers for beer,” and “Polyclar® stabilizersfor wine.” Polyclar® Brewbrite™ also is described in an article byRehmanji, et al. (2002), which also is incorporated in its entirety byreference.

PVPP is offered for sale by BASF Corp. (Ludwigshafen, Del.) in theKollidon® CL and Luvicross® product lines. Four grades ofpharmaceutical-grade crospovidone compose the Kollidon® CL line: CL,CL-M, CL-F, and CL-SF. The industrial grade of PVPP is sold under theLuvicross® name.

In addition, PVPP of the Sunvidone CL series is sold by HangzhouSunflower Technology Development Co. (Hangzhou, Conn.). Three grades areavailable, CL-10, CL-30, and CL-100.

In commercial applications, PVPP dust can be problematic as containers(e.g., bags, drums) are emptied and the product filled into hoppers,bins, and used in process equipment. PVPP dust can be collect in theseareas where it may manifest itself as cohesive, fine particles that canbe difficult to handle and/or settle onto non-target surfaces, unlikethe majority of the PVPP product that flows like a granular solid. Suchbehavior is related to the PVPP particle size distribution. Thisnuisance may be encountered by smaller-sized companies lackingsophisticated and potentially expensive materials handling equipment.

Such PVPP of small particle size may represent a material loss for thecustomer. It may be disposed as waste, and may contribute tohousekeeping problems. Hence, there is the need for PVPP products thatminimize these material handling issues while maintaining productperformance without the need for special handling equipment.

In the beer industry where PVPP is valued as a polyphenol absorber,product performance is directly related to particle size. The work ofMcMurrough et al. (J Agricult Food Chem, 43, 10, 2687-2691, 1995)showed, “the adsorptive capacity of commercial PVPP increased withdecreasing particle size.”

Related to beer stabilization and purification is U.S. Pat. No.4,820,420, which teaches a centrifugal method for removing polyphenolsand/or proteins. The disclosure includes a process in which “kieselguhr,perlite, cellulose, and synthetic fibers or granulated cellulose orsynthetic materials are used as filter means.” However, there is nodisclosure for a granulated composition containing 15% or more PVPP.

U.S. Pat. No. 4,695,397 teaches a granular bleaching activator thatcomprises PVPP. This bleaching activator contains from 2.5 parts to 15parts of a water-swellable assistant, which may be PVPP. U.S. Pat. No.4,840,799 discloses a process for preparing a rapidly disintegrating,pharmaceutical core wherein a granulate is formed that may comprise PVPPin an amount of 2%-15% (w/w). Again, neither patent discloses agranulated compositions having 15% or more PVPP.

Turning to laundry applications, U.S. Pat. No. 6,900,165 disclosescompact, particulate laundry detergents comprising PVPP of a specificparticle size distribution. In the compressed laundry tablet, PVPP ispresent between about 0.5%-20% of the overall mass of thedetergent/cleaning product. The aforementioned particle sizedistribution is as follows:

not more than 10% (w/w) of the PVPP particles have a size less than 63μm,

-   -   not more than 30% (w/w) and at least 0.1% (w/w) of the PVPP        particle have a size greater than 1000 μm, and    -   at least 10% (w/w) of the PVPP particles have a size less than        200 μm.

Further, the prior art broadly teaches numerous blends having PVPP thatare then granulated, including pharmaceutical granulations blended withcrospovidone prior to tableting. For example, a rapidly disintegratingtablet comprising a compressed granulate is taught in U.S. Pat. No.7,282,217. However, a disintegrant, such as crospovidone, as added tothe granulate prior to tableting. While PVPP dusting may be experienced,the prior art does not provide solutions to this problem.

Despite the wide use of PVPP in the beverage, cleaning, andpharmaceutical sciences arts, no one has addressed the PVPP dustingproblem that exists during material handling operations, particularlywith solutions that do not sacrifice the binding capacity of thiscrosslinked polymer. Additionally, no one has recognized potentialbenefits in related areas when the dusting problem is resolved by theapproach embraced by the current invention.

SUMMARY

In a first embodiment of the invention, low-dusting PVPP compositionsare provided by compressing a feed comprising PVPP, and then breakingthe compressed composition into granules or grains. Particles sized 100μm and smaller make up less than 10% (w/w) of the granulated PVPPcomposition immediately following the compression step. In preferredembodiments, particles sized 100 μm and smaller make up less than 5%(w/w) of the granulated PVPP composition. In highly preferredembodiments, particles sized 170 μm and smaller make up less than 10%(w/w) of the granulated PVPP composition.

The PVPP granulated product comprises at least about 15% PVPP, and morepreferably comprise about 30% or more PVPP. Highly preferred embodimentsof the invention comprise about 70% or more PVPP.

The invention also claims methods for producing the abovementionedgranulated PVPP compositions, having the steps: (A) compressing afeedstock comprising PVPP, and, (B) breaking the compressed feedstockinto granules, grains or a powder. In an especially preferredembodiment, the compression step is performed by a roller compactor oran extruder. In a separate, especially preferred embodiment, thebreaking step is performed by granulating and/or milling operations.

In another embodiment of the invention, granulated PVPP compositions areused in the production and/or treatment of beverages. In especiallypreferred embodiments, the granulated PVPP compositions are employed toclarify, stabilize, and/or remove polyphenols from beverages like wine,beer, and tea.

In yet another embodiment of the invention, PVPP is admixed with one ormore co-ingredient(s) prior to or during the compressing and/or breakingsteps described above. By doing so, any number of formulary ingredientscan be combined with PVPP in order to enhance material handling andperformance compared to PVPP grades that currently exist. Thesecompositions offer the end user the benefits of reduced dusting andeasier materials handling and all-in-one product performance whencompared to the individual components. Preferred examples of thisembodiment include PVPP and cellulose granules, PVPP and bentonite claygranules, and PVPP with cellulose and bentonite clay granules.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of the process of Example 1.

FIG. 2 is a photograph of a composition produced in accordance withExample 1.

FIG. 3 is a photograph of a composition produced in accordance withExample 1.

FIG. 4 is a photograph of a composition produced in accordance withExample 1.

FIG. 5 is a graph describing a particle size distribution of acomposition produced in accordance with Example 5.

FIG. 6 is a graph describing a particle size distribution of acomposition produced in accordance with Example 6.

FIGS. 7-9 are photographs of granulated compositions produced inaccordance with Example 7.

FIGS. 10 and 11 are graphs describing particle size distributions ofcompositions produced in accordance with Example 7.

FIG. 12 is a graph of total polyphenol index-white wine for threegranular compositions at three dose rates in accordance with Example 8.

FIGS. 13A and 13B are graphs of white wine absorbance at 520 nm(“pinking”) as a function of time for three granular compositions inaccordance with Example 9.

FIGS. 14A and 14B are graphs of white wine absorbance at 420 nm(“browning”) as a function of time for three granular compositions inaccordance with Example 10.

FIGS. 15A and 15B are graphs of white wine haze as a function of timefor three granular compositions in accordance with Example 11.

FIG. 16 is a graph of total polyphenol index-red wine for three granularcompositions at three dose rates in accordance with Example 12.

FIGS. 17A and 1713 are graphs of red wine absorbance at 420 nm (“color”)as a function of time for three granular compositions in accordance withExample 13.

DETAILED DESCRIPTION

All percentages, ratio, and proportions used herein are based on aweight basis unless other specified.

Low-dusting PVPP compositions are provided by this invention thatresolve the dust problems that are generated from current PVPP gradesand products comprising PVPP. A feedstock having PVPP is firstcompressed and then broken to form granules, grains, or particles. Asubstantially dust-free product can be produced by returning to thefeedstock a fraction of the product that is undersize for re-compressionprocessing. Thus, the low dusting PVPP compositions of nearly anyparticle size target can be made and then used without special materialhandling equipment.

When used in beverage applications, it was unexpected that thegranulated PVPP products can be substantially free of PVPP dust and yetmaintain the original polyphenol absorptive capacity of the unprocessedPVPP feedstock.

In a first embodiment, the feedstock and granulated product consistentirely of PVPP. This low-dusting product can be used alone or incombination with other products in a variety of application arts. Forexample, the granules may be added to columns used to remove polyphenolsduring the manufacture of beverages, especially beverages that are madefrom various grains (e.g., wheat, barley, rice), fruits (e.g., grapes),tea (e.g., green tea), or blends thereof. These beverages typicallycontain polyphenols and/or proteins, the removal of which may improvethe aesthetic or sensory characteristics of the beverage. Thesebeverages may be alcoholic, like wine and beer, or non-alcoholic, likefruit juices and teas.

In a second embodiment, the feedstock comprises PVPP blended withco-ingredients that are selected in order to impart new functionalityinto the product. Such co-ingredients may convey benefits such asincreased and/or new absorptive capacity, compressibility improvement,controlled particle size distribution, and/or enhanced disintegration ofsubsequent compacted products. For example, co-ingredients likecellulose fiber and/or bentonite clay may be blended with PVPP,co-compressed, and then broken into granules for use in wine making. Notonly are these granules low-dusting, but they also offer convenience tothe wine maker for removing polyphenols and proteins in a singleprocessing aide. As shown in the Examples section, the granulatedcompositions retain 80% or more of the original polyphenol removal ofthe ungranulated feedstock. Exemplary PVPP granules of the inventionretain about 90% or more, or even about 95% or more of the ungranulatedpolyphenol absorptivity.

It was briefly mentioned earlier that the PVPP-containing compositionsare produced from a first compression step performed using methods thatare known and/or commercially available. This step aims to consolidateessentially all the feedstock particles into a coherent mass. Also,undersize product can be returned to this step for recompression, whichsignificantly aides in achieving low-dusting product.

Methods capable of performing this compression step include (withoutlimitation): roller compaction, extrusion, and slugging. Rollercompactors operate with rotating rolls forming a nip into which the feedis introduced. Feed rate, roll cover material, surface temperature,speed, and compression force are selected per final productrequirements. Commercially-available roller compactor equipment include:TFC roll compaction systems from Vector Corporation (Marion, Iowa), theWP series roller compactor and granulator line of Alexanderwerk, Inc.(Horsham, Pa.), and RC model roller compactors from Powtec Maschinen andEngineering GmbH (Remseheid, Germany).

Extrusion also may be employed in which feed is compacted and forcedthrough a die either at or near room temperature (“cold extrusion”) orat elevated temperature (“hot extrusion”). Direct and indirect extrudersare known in the art, and include models by Advanced ExtruderTechnologies (Elk Grove Village, Ill.), and Wayne Machine & Die Company(Totowa, N.J.).

Slugging is a generic term for compressing materials, typically usingdies as in a press such as a tablet or hydraulic press. Examples of asuitable hydraulic presses include the series of presses by Carver, Inc.(Wabash, Ind.).

In addition to this first compression step, a second step is providedfor breaking the compressed composition into discrete pieces, such asgranules, grains, and powders (“breaking step”). In a preferredembodiment, this second step is performed by a granulator or a mill.Such equipment is commercially available from numerous companies,including: granulators by Sterling (New Berlin, Wis.), granulators byRapid Granulator, Inc. (Rockford, Ill.), hammer mills and size reductionequipment by Williams Crusher, Inc. (St. Louis, Mo.), and mills fromStedman Machine Co. (Aurora, Ind.).

The granules, grains, and/or powders produced after this breaking stepexhibit reduced dusting compared to the starting feed. Within thecontext of “reduced dusting,” particles 100 μm or smaller make up 10%(w/w) or less of the granulated product, more preferably particles 100μm or smaller make up 5% (w/w) or less of the granulated product, and inespecially preferred embodiments, particles 170 μm or smaller make upless than 10% of the product. The mean particle size and particle sizedistribution conforming to the “reduced dusting” description can beattained by controlling factors related to the first and second steps.For example, prior to the compression step the feedstock can beformulated to affect its compression and friability. The compressionstep can be regulated with respect to pre-compression force (if any),pre-compression dwell time (if any), compression force, and compressiondwell time. Similarly, parameters related to the breaking step can bechosen to control the final product particle size and particle sizedistribution. If a granulator is employed to break the compressedfeedstock, then parameters like feed rate, blade type, blade speed, andexit screen mesh (size) can be selected to achieve the target granulesize specifications. For operational efficiency, it is preferred (butnot required) that process operations be optimized so that a majority ofthe product with the desired particle size and particle sizedistribution exits the one or more exit screens. However, it is possibleto achieve these particle size specifications through judicious choiceof the exit screens, discarding or recycling any undersize or oversizefraction.

For economic reasons, it is preferred (but not required) that anyundersize or oversize fraction from this step be returned forre-compression. If this in-process recycle step is employed whenco-ingredients are added to the PVPP feedstock, then it may be necessaryto monitor ingredient ratios in the final product so that the targetcomposition specification is attained.

As mentioned, particles 100 μm and smaller make up 10% (w/w) or less ofthe granulated composition. However, because the compression andbreaking steps can be operated within a wide working range, the productis typically larger than 100 μm, for example, greater than 200 μm, andeven greater than 400 μm. It is evident that these larger granulesobvious any dusting concern as exhibited by the unprocessed startingmaterial.

Determination of the particle size may be made by methods known in theart, provided that an adequate sample is selected for measurement andproperly handled so that represents the product after its production

It may be preferred to perform the compression and breaking steps usingone piece of process equipment. Equipment to provide benefits in time,material handling, product quality, and product yield are known, andinclude the Chilsonator® by the Fitzpatrick Co. (Elmhurst, Ill.).

Depending on the types of process equipment, their operation, and thedesired reduction in product dust, it may be advantageous to sizefractionate material exiting the breaking process step and return to thefeedstock an undersized fraction for additional compression processing.Such size fractionation may be accomplished using known methods, such asscreening using sieve(s) of a desired mesh.

It has been surprisingly discovered that additional co-ingredients canbe added to the feedstock to produce not only a low-dust product, butproducts of increased functionality. The methods and compositions of theinvention are utile when the co-ingredient(s) exhibit dustingtendencies, especially if the particle size of the uncompressedco-ingredient is about 100 μm or less. Such products exhibit propertiesnot achieved when PVPP is processed alone. Such additional materialsinclude, without limitation: absorbents, active ingredients, adsorbents,beverage process aides, binders, complexation aides disintegrants,disintegrant aides, lubricants, plasticizers, polyphenol absorbers,protein absorbers, stabilizers, surfactants, wetting agents, and wickingagents.

Absorbents and adsorbents are those materials that absorb substances orcause substances to accumulate on the surface. Absorbents/adsorbentsexhibit reversible or permanent complexation interactions with thesubstance, e.g., through hydrogen bonding and/or dipole interaction.Absorbents and adsorbents are commonly used in the chemical arts ascarriers, clarifiers, and purifiers. They are known by beer, fruitjuice, and wine manufacturers for their ability to improve beveragetaste, color, and shelf life. Examples of absorbents and adsorbents usedin the beverage industry include, in addition to PVPP: activated carbon,bentonite clay, carrageenan, diatomaceous earth, polysaccharides, andsilica xerogel. Unlike PVPP, which exhibits affinity for polyphenolcomplexation, these absorbents/adsorbents selectively absorb proteins,and, for example, find extensive use in the manufacture of white wine.

Absorbents/adsorbents also are used in the laundry, ink, and printingarts where they fix a target compound(s) in order to avoid colorbleeding, release, and transfer. Examples of complexation aides includeco- and terpolymers of dimethylaminopropylmethacrylamide, such asViviPrint™ 200 and 300; polyvinylpyrrolidone, such as Plasdone® grades(all International Specialty Products); and amorphous silica gel, suchas Silcron® IJ-50 (Millennium Chemicals). The utility of co-compressingPVPP with other absorbents/adsorbents is self apparent.

In the beverage industry, kappa-carrageenan, bentonite clay and silicas(e.g., silica xerogel, silica hydrogel, silica aerogel, and silica sol)are complexation aides that are useful for the removal of haze-producingdrink constituents. Kappa-carrageenan is a hydrocolloid extract from redseaweed that is very effective at reducing non-microbiological particles(e.g., proteins, polyphenols, and polysaccharides) from wort.Non-biological haze results primarily from the hydrogen bonding betweenhaze-producing proteins and polyphenol constituents of beer.

Bentonite clay is an aluminosilicate that effectively removes proteinsfrom white wine. It consists principally of montmorillonite with variousimpurities, such as kaolinite. As an absorbent, bentonite can removelarge amount of proteins that otherwise denature and precipitate duringwine aging and/or when brought to room temperature.

Silica xerogel is another non-additive absorbent used together with PVPPin the beverage industry. Silica xerogels are free-flowing,non-crystalline (amorphous) silicon dioxide that is also known by thesynonym silica gel. Silica xerogels are employed by brewers to removehaze-producing proteins.

In addition to beverage process aides, active ingredients may beincluded for use in this invention. Active ingredients are defined asthose chemical compounds that elicit a response due to their chemicalnature. Categories of actives include biocides, fertilizers, fragrances,nutritionals, pharmaceuticals, and reactants. When co-compressed withPVPP to product low-dusting, granular products, active ingredients mayexhibit enhanced solubility and/or bioavailability. In preferredembodiments, the active ingredient is a biocide, a fertilizer, anutritional, or a pharmaceutical active.

Within this context, biocide refers any composition that kills life bypoisoning it, and includes: algaecides, aquaticides, insecticides,fungicides, germicides, herbicides, larvicides, pesticides, rodentcides,and taeniacides. It is noted that both organic and inorganic materialsexhibit biocidal activity.

Examples of algaecides/fungicides/mildewcides include:3-allyloxy-1,2-benzoisothiazol-1,1-dioxide; basic copper chloride; basiccopper sulfate; 1,2-benzisothiazoline-3-one;methyl-N-(1H-benzoimidazol-2-yl)carbamate (carbendazim);2-(tert-butylamino)-4-(cyclopropylamino)-6-(methylthio)-s-triazine(Irgarol®); 2-tert-butylamino-4-ethylamino-6-methylmercapto-s-triazine(terbutryin);S—N-butyl-5′-para-tert-butylbenzyl-N-3-pyridyldithiocarbonylimidate;2-chloro-1-(3-ethoxy-4-nitrophenoxy)-4-(trifluoromethyl)benzene(oxyfluorfen);4-chlorophenoxy-3,3-dimethyl-1-(1H,1,3,4-triazol-1-yl)-2-butanone;α-[2-(4-chlorophenyl)ethyl]-α-(1,1-dimethylethyl)-1H-1,2,4-triazole-1-ethanol(tebuconazole); copper 8-quinolinate; cycloheximide;bis-(dimethyldithiocarbamoyl)disulfide; 11-dehydrodibenzo(b,f)azepine;2,4-dichloro-6-(0-chloroanilino)-1,3,5-triazine;1,4-dichloro-2,5-dimethoxybenzene;N′-dichlorofluoromethylthio-N,N-dimethyl-N-phenyl sulfamide;2,3-dichloro-1,4-naphthoquinone; 2,6-dichloro-4-nitroaniline;4,5-dichloro-2-N-octyl-4-isothiazolin-3-one (DCOIT);N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboxylmide;N′-(3,4-dichlorophenyl)-N,N-dimethylurea (diuron);1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxorane-2-ylmethyl]-1H,1,2,4-triazol;N-(3,5-dichlorophenyl) succinamide;1-[[2(2,4-dichlorophenyl)-4-propyl-1,3-dioxolan-2-yl]methyl]1-H-1,2,4-triazole(propiconazole); N-2,3-dichlorophenyltetrachlorophthalamic acid;3-(3,5-dichlorophenyl)-5-ethenyl5-methyloxazolizine-2,4-dione;2,3-dicyano-1,4-dithioanthraquinone;N-(2,6-diethylphenyl)-4-methylphthalimide;N-(2,6-p-diethylphenyl)phthalimide;5,6-dihydro-2-methyl-1,4-oxathine-3-carboxanilide;5,6-dihydro-2-methyl-1,4-oxathine-3-carboxanilido-4,4-dioxide;diisopropyl 1,3-dithiolane-2-iridene malonate; O,O-diisopropylS-benzylphosphorothioate;2-dimethylamino-4-methyl-5-N-butyl-6-hydroxypyrimidine;bis-(dimethyldithiocarbamoyl)ethylenediamine;5-ethoxy-3-trichloromethyl-1,2,4-thiaziazole; ethyl-N-(3-dimethylaminopropyl)thiocarbamate hydrochloride; O-ethylS,S-diphenyldithiophosphate;3,3′-ethylene-bis-(tetrahydro-4,6-dimethyl-2H-1,3,5-thiadiazine-2-thione);3-hydroxy-5-methylisooxazole; 3-iodo-2-propargyl butyl carbamate (IPBC);irgarol, iron methanearsonate; 3′-isopropoxy-2-methylbenzanilide;1-isopropylcarbamoyl-3-(3,5-dichlorophenyl)hydantoin; kasugamycin;manganese ethylene-bis-(dithiocarbamate);1,2-bis-(3-methoxycarbonyl-2-thioureido) benzene;methyl-1(butylcarbamoyl)-2-benzimidazolecarbamate;5-methyl-10-butoxycarbonylamino-10; 3-methyl-4-chlorobenzthiazol-2-one;methyl-D,L-N-(2,6-dimethylphenyl)-N-(2′-methoxyacetyl)alaninate;S,S-6-methylquinoxaline-2,3-di-yldithiocarbonate5-methyl-s-triazol-(3,4-b)benzthiazole; nickel dimethyldithiocarbamate;2-octyl-2H-isothiazol-3-one (OIT); 2-oxy-3-chloro-1,4-naphthoquinonecopper sulfate; pentachloronitrobenzene;(3-phenoxyphenyl)methyl(+/−)-cis,trans-3-(2,2-dichloroethenyl)-2,2-dimethylcyclopropanecarboxylate(permethrin); piomycin; polyoxine; potassiumN-hydroxymethyl-N-methyldithiocarbamate;N-propyl-N-[2-(2,4,6-trichlorophenoxy)ethyl]imidazol-1-carboxamide;2-pyridinethiol-1-oxide sodium salt; sodium pyrithione;N-tetrachloroethylthio-4-cyclohexene-1,2-dicarboxylmide;tetrachloroisophthalonitrile; 4,5,6,7-tetrachlorophthalide;1,2,5,6-tetrahydro-4H-pyrrolo[3,2,1-i,j]quinoline-2-one;2-(thiocyanomethylthio)benzothiazole; N-trichloromethylthio4-cyclohexene-1,2-dicarboxyimide; N-(trichloromethylthio)phthalimide;validamycin; zinc ethylene-bis-(dithiocarbamate); zincbis-(1-hydroxy-2(1H)pyridinethionate; zincpropylene-bis-(dithiocarbamate); and zinc pyrithione.

Commercial examples of biocides include (in alphabetical order): aminereaction products (Nuosept® 145), 1,2-benzisothiazolin-3-one (Nuosept®495, 497, 498), 2-bromo-2-nitropropane-1,3-diol (bronopol) (Nuosept®330), 3-iodo-2-propargyl butyl carbamate (IPBC) (Fungitrol® 440S, 400SE,420S, 430S, 440S, 720, 920, 930, 940),5-chloro-2-methyl-4-isothiazolin-3-one(CMIT)/2-methyl-4-isothiazoli-3-one (MIT) (Nuosept® 515R), bicyclicoxazolidines (Nuosept® 95), glutaraldehyde (Nuosept® 210),N-(trichloromethylthio)phthalimide biocides (folpet) (Fungitrol® 11 and11-50S, PlastiGuard® 11 PE), tetrachloroisophthalo-nitrile biocides(Fungitrol® 404-D and 960),tetrahydro-3,5-dimethyl-2h-1,3,5-thiodiazine-2-thione (Nuosept® S), alloffered for sale by International Specialty Products (Wayne, N.J.).

A plant growth regulators are a chemical compound that alters the growthand/or the productivity of plants, and comprise herbicides andfertilizers. Plant growth regulators include inorganic and organicfertilizers, and contain micro- and macronutrients such as ammonia,urea, ammonium nitrate, ammonium sulfate, and compounds containingmagnesium, nitrogen, phosphorus, and potassium. Examples of plant growthregulators include:N-methoxycaronyl-N′-4-methylphenylcarbamoylethylisourea;1-(4-chlorophenylcarbamoyl)-3-ethoxycarbonyl-2-methylisourea; sodiumnaphthaleneacetate; 1,2-dihydropyridazine-3,6-dione; and gibberellins.

Examples of herbicides include (in alphabetical order):5-bromo-3-sec-butyl-6-methyluracil;5-tert-butyl-3-(2,4-dichloro-5-isopropoxyphenyl)-1,3,4-oxadiazoline-2-one;S-(4-chlorobenzyl)-N,N-diethylthiolcarbamate;2-chloro-4,6-bisethylamino-1,3,5-triazine;2-chloro-2′,6′-diethyl-N-(butoxymethyl)acetoanilide;2-chloro-2′,6′-diethyl-N-(methoxymethyl)acetoanilide;2-chloro-4-ethylamino-6-isopropylamino-s-triazine;2-chloro-4-methylphenoxyacetic acid; 4-chloro-2-methylphenoxyaceticacid; 3-(4-chlorophenyl)-1,1-dimethyl urea;1-cyclohexyl-3,5-propyleneuracil; 2,4-dichlorophenoxyacetic acid, andmethyl-, ethyl-, and butyl-esters thereof.;3-(3,4-dichlorophenyl)-1,1-dimethylurea;3-(3,4-dichlorophenyl)-1-methoxy-1-methyl urea;2,4-dichlorophenyl-4′-nitrophenylether; 3,4-dichloropropioneanilide;N[3],N[3]-diethyl-2,4-dinitro-6trifluoromethyl-1,3-phenylene diamine;1,1′-di-methyl-4,4′-bis-pyridinium dichloride;1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-hydroxypyrazole;1,3-dimethyl-4-(2,4-dichlorobenzoyl)-5-(p-toluenesulfonyloxy)pyrazole;3,5-dimethylphenyl-4′-nitrophenylether; diphenylether ethyl2-methyl-4-chlorophenoxybutylate;S-ethyl-N-cyclohexyl-N-ethylthiolcarbamate;S-ethyl-hexahydro-1H-azepine-1-carbothioate;S-ethyl-N,N-di-N-propyl-thiocarbamate;3-isopropylbenzo-2-thia-1,3-diazinone-(4)-2,4-dioxide;2-[N-isopropyl,N-(4-chlorophenyl)carbamoyl]-4-chloro-5-methyl-4-isooxazoline-3-one;isopropyl-N-(3-chlorophenyl)carbamate;3-methoxycarbonylaminophenyl-N-(3-methylphenyl)carbamate;2-methoxy-4-ethylamino-6-isopropylamino-1,3,5-triazine;methyl-N-(3,4′-dichlorophenyl)carbamate; 3-(2-methyl-phenoxy)pyridazine4-(methylsulfonyl)-2,6-dinitro-N,N-dipropylaniline;2-methylthio-4,6-bis-ethylamino-1,3,5-triazine;2-methylthio-4-ethylamino-6-isopropylamino-s-triazine;2-methylthio-4,6-bis-(isopropylamino)-S-triazine;N-(phosphonomethyl)glycine; 2,4,6-trichlorophenyl-4′-nitrophenylether;and α,α,α-trifluoro-2,6-dinitro-N,N-dipropyl-p-toluidine.

Binder are chemical compositions that cause components of a mixture tostick (or bind) together, and may be included for compression with PVPPin the feedstock. It is envisioned that binders may find specialapplication for granulated compositions comprising PVPP; binders helpcreate a consolidated mass after compression, especially when poorlycompressible co-ingredients are added to feedstock comprising PVPP. Manybinders are known in the prior art, and are limited only inasmuch asthey be suitable for the final product, the intended application, andproduct attributes. Specific examples of binders include, withoutlimitation (in alphabetical order): acacia, celluloses, lactoses, oils,polyols, polysaccharides, polyvinylpyrrolidones, starches, andtragacanth, and their respective derivatives.

Disintegrant aides and wicking agents may be included with PVPP in thefeedstock. Disintegrant aides are those materials that assist in thebreak-up of compressed forms, wherein wicking agents serve to transportliquids, especially water, by virtue of their form and chemicalcomposition. Both disintegrant aides and wicking agents are widely usedin compressed and uncompressed product forms, such as tablets andcapsules/sachets. Examples of disintegrant aides and wicking agentsinclude: alginic acid, calcium silicate, carboxymethylcellulose sodium,celluloses (e.g., microcrystalline and powdered), chitosan, colloidalsilicon dioxide, croscarmellose sodium, guar gum,hydroxypropylcellulose, magnesium aluminum silicate, methylcellulose,polacrilin potassium, sodium alginate, sodium bicarbonate, sodium starchglycolate, and starch. Pharmaceutically-approved disintegrant aides andwicking agents are described in The Handbook of PharmaceuticalExcipients by R. C. Rowe, P. J. Sheskey, and S. C. Owen (PharmaceuticalPress and American Pharmaceutical Association, 2003), which isincorporated in its entirety by reference.

It is envisioned that the feedstock comprising PVPP may be directlycompressed “as is.” Yet, it is also contemplated that humidification ofthe feedstock may assist the compression step and yield product furtherreduced in fines content. Water is a known plasticizer, meaning itlowers the glass transition temperature of non-crystalline materials.Humidification may improve the compressibility of the feedstock, and mayprove helpful if the blended co-ingredients require improvedcompressibility. It is preferred that humidification (if any) of thefeedstock be sufficient to promote compressibility without causingprocessing difficulties such as roll sticking. Furthermore, it isrecognized that feedstock humidification may be attained simply byvirtue of where the materials are stored, e.g., a warehouse orprocessing floor of sufficient humidity, especially for hygroscopicand/or hydrophilic feedstock materials (e.g., PVPP).

Additionally, it is contemplated that the feedstock may comprise otherplasticizers to enhance the plastic properties of feedstock composition,for example, increasing flexibility and/or durability by lowering theglass transition temperature (T_(g)) of the composition. Other examplesof such plasticizers include (in alphabetical order): citrates (e.g.,acetyltributyl, acetyltriethyl, tributyl, and triethyl citrates),glycols (e.g., polyethylene glycol and propylene glycol, glycerin),medium-chain triglycerides (e.g., mixtures of caprylic acid and capricacid), phthalates (e.g., dibutyl, diethyl, and dimethyl phthalates),stearates (e.g., glyceryl monostearate), and triacetin. The necessaryplasticizer addition level is dependent on the degree of plasticizationneeded.

Yet other co-ingredients may be included with PVPP in the feedstock forcompression processing.

The invention will now be described with particular reference to thefollowing non-limiting examples:

EXAMPLES Example I

Two grades of food-grade PVPP, Polyclar® XG and Polyclar® 10(International Specialty Products), were individually compressed using aTF Mini Roller Compactor (Vector Corporation, Marion, Iowa) operatingwith a screw speed of about 83 rpm, a roller speed of 6.5 rpm, and aroller pressure of 4 tons.

The resultant ribbons from the roller compactor were granulated using anErweka® AR400 Oscillating Granulator (Heusenstamm, Germany). Thegranular solid products were size fractionated using 10 mesh and 18 meshscreens. Product passing through the 18 mesh screen (“fines”) wasreturned to the feed for re-compression processing.

FIG. 1 presents a schematic diagram of the process, wherein

-   -   Item A represents the feedstock bin.    -   Item B represents the auger feeder system.    -   Item C represents the roller compacter rolls and the nip they        form (at arrow).    -   Item D represents the compressed ribbon exiting the rollers.    -   Item E represents the granulator.    -   Item F represents a first screen at the exit of the granulator.    -   Item G represents granulated product having a size smaller than        the mesh of screen F, but larger than the mesh of screen H.    -   Item H represents a second screen, finer than screen F, for        fines removal.    -   Item I represents undersize product that passed through the        second screen (Item H) that is redirected back to the feedstock        bin for additional compression processing.

A photograph of a compressed PVPP ribbon is shown in FIG. 2.

Granular, low-dusting PVPP product was produced upon discharge from thegranulator. Photographs of the two lots of granular products areillustrated in FIGS. 3 and 4, wherein the shown ruler is a standardmetric ruler with 1-mm gradations.

Example 2

The dry and hydrated particle size distributions were measured for thetwo product lots produced in Example 1. A Malvern Mastersizer S (MalvernInstruments Ltd., Worcestershire, UK) was employed with a range lens of300 mm, a beam length of 10.00 mm, a particle refractive index of1.729+i0.1000, a dispersant (air) refractive index of 1.000+i0.000, and5000 sweeps.

Upon rehydration, the granular products disintegrated to almost theoriginal particle size distribution of the unprocessed feedstock PVPP(Table 1).

TABLE 1 Particle size distribution results of Example 2. particle sizedistributions (μm) material state of material d_(10%) d_(50%) d_(90%)span Polyclar ® XG feedstock powder: 6.1 11.5 18.2 1.0 unprocessed, dryfeedstock powder: 2.9 14.3 23.8 1.5 unprocessed, hydrated compressed +granulated 5.0 18.2 44.4 2.2 product: 10 mesh, hydrated compressed +granulated 4.5 16.6 37.8 2.0 product: 18 mesh, hydrated Polyclar ® 10feedstock powder: 12.7 23.9 42.9 1.3 unprocessed, dry feedstock powder:9.0 30.1 76.3 2.2 unprocessed, hydrated compressed + granulated 8.6 30.482.3 2.4 product: 10 mesh, hydrated compressed + granulated 8.3 30.181.9 2.4 product: 18 mesh, hydrated

Method 1: Catechin (a Polyphenol) Absorption Test

Standard Solution: In an amber volumetric flask 80 mg catechin hydrate(+catechin hydrate, Aldrich Chemical Company, Milwaukee, Wis.) wasdissolved in 50 mL of ethanol, which was then diluted 1 L with distilledwater.

Reference Solution: In a volumetric flask 50 mL ethanol (absolute) wasdiluted to 1 L with distilled water.

Water content of beverage treatment aide: The water content of the PVPPbeverage aide was determined using Karl Fisher analysis.

Test Solutions (in duplicate): A 50 mg sample of beverage treatment aide(weight corrected for moisture content) was weighed and added to abeaker containing a Teflon® magnetic stir bar. To this beaker was added100 mL of Standard Solution and the sample was stirred by the magneticstir bar. After exactly 5 minutes of stirring, an aliquot was withdrawnwas passed through a 0.45 μm Teflon® filter. The filtered sample wasstored in a cool, dark place for a maximum of 1 hour before measuringthe UV absorbance.

Blank Solution: A 50 mg sample of beverage treatment aide (weightcorrected for moisture content by Karl Fisher analysis) was weighed andadded to a beaker containing a Teflon® magnetic stir bar. To this beakerwas added 100 mL of Reference Solution and the sample was stirred by themagnetic stir bar. After exactly 5 minutes of stirring, an aliquot waswithdrawn was passed through a 0.45 μm Teflon® filter. The filteredsample was stored in a cool, dark place for a maximum of 1 hour beforemeasuring the UV absorbance.

The absorbances were measured for the two filtered Test Solution and theBlank Solution aliquots using 1 cm quartz cuvettes at 280 nm using aPerkin Elmer spectrophotometer, model 559A (Waltham, Mass.). TheReference Solution was used to zero the spectrophotometer, and served asthe reference for each filtered sample.

The polyphenol absorption of the beverage treatment aide was calculatedas:

$A = {\frac{A_{o} - ( {A_{\tau} - A_{b}} )}{A_{o}} \times 100}$

wherein:

A_(o) is the polyphenol absorption of the Standard Solution,

A_(r) is the polyphenol absorption of the Test Solution, and

A_(b) is the polyphenol absorption of the Blank Solution,

The average of the two Test Solutions was reported for each beveragetreatment aide.

Example 3

The adsorptive capacity was measured by Method 1 for the untreated andtreated lots of Example 1.

Contrary to expectation, no loss in adsorptive capacity was measured forthe granulated, low-dusting PVPP products (Table 2).

TABLE 2 Adsorptive capacity results of Example 3. polyphenol PVPP gradetest material absorption Polyclar ® XG uncompressed feedstock powder60.2% compressed + granulated product: 10 mesh 59.8% compressed +granulated product: 18 mesh 60.8% Polyclar ® 10 uncompressed feedstockpowder 56.1% compressed + granulated product: 10 mesh 55.9% compressed +granulated product: 18 mesh 55.1%

Method 2: Measurement of Haze-Producing Polyphenols and Proteins

The PT Standard automatic titrator made by OPTO-EMS (Dannstadt, Germany)was used to measure the content of haze-producing polyphenols andproteins. This instrument automatically doses a reagent specific topolyphenols (T125, a proprietary reagent based on polyvinylpyrrolidone)or proteins (P40, a proprietary reagent based on ammonium sulfate).These reagents form complexes with polyphenol and “salt out” proteins,respectively, to quantify their content in beverages. In each case theresulting beverage haze initially increases with reagent addition, thendecreases. The reported value coincides with the maximum haze of a testsample.

Beer test solution: Granulated beverage treatment aide (e.g., granulatedPVPP) was weighed and added to a beaker containing a Teflon® magneticstir bar.

To the beverage treatment aide was a beer sample, and the sample wasstirred by the magnetic stir bar.

After exactly 5 minutes of stirring, an aliquot was withdrawn was passedthrough a 0.45 μm filter.

A 4-mL sample of filtered beer was added to a clean PT Standard cuvette,which was placed in the measurement chamber and the dosing headpositions.

After a 30-second equilibration, the instrument was zeroed to obtain thereference haze value.

The titration was initiated by clicking, “start” using either the P40reagent (for protein analysis) or the T125 reagent (for polyphenolanalysis).

Automatic titration and haze measurement was performed by the PTStandard instrument to a pre-programmed haze value is attained.

Results are reported in units of “mL reagent/100 mL beer.” Increasingvalues indicate increased reagent demands, and therefore increasing beerstability.

Example 4

Method 2 was applied to measure the absorptive performance for sixgranulated beverage treatment aides. American-style lager was tested at10 g PVPP/hL (=100 mg PVPP/L).

No loss in haze stability was measured using the compositions producedin Example 1 (Table 3).

TABLE 3 Haze stability titers of Example 4. titer value (mL) T-125reagent P-40 reagent material test material (polyphenols) (proteins)Polyclar ® XG feedstock powder 40.8 34.8 compressed + granulated 39.734.6 product: 10 mesh compressed + granulated 39.1 35.2 product: 18 meshPolyclar ® 10 feedstock powder 34.1 33.7 compressed + granulated 32.134.1 product: 10 mesh compressed + granulated 32.7 33.4 product: 18 meshuntreated beer 12.4 32.6

Example 5

The particle size distribution of a crosslinked polyvinylpyrrolidone,sold under the trade name Polyclar® 10 (International SpecialtyProducts), was analyzed in the dry state by a light-scattering technique(Malvern Instruments, Malvern, UK). The results indicate that the 50thpercentile particle size (d₅₀) was about 23 μm (FIG. 5). About 10% ofthe particles were smaller than 10 μm.

The described lot of Polyclar® 10 was dry roller compacted by aChilsonator® (Fitzpatrick Company, Elmhurst, Ill.) operating with bothhorizontal and vertical feed augers. The compaction roller space wasadjusted so that a compacted PVPP ribbon was produced.

The compressed ribbon was fed to a hammer mill to granulate thecompressed product. Product was discharged from the mill through a 10mesh screen onto a vibratory screener fitted with either a 20 mesh or 42screen.

Example 6

The dry, granular product of Example 5 was size fractionated using aRo-Tap rotary tapping sieve shaker (Laval Lab, Inc, Quebec, Calif.)equipped with four screens: 80 mesh (0.178 mm), 40 mesh (0.422 mm), 20mesh (0.854 mm), and 10 mesh (2.06 mm) screens.

No granular product was retained on the 10 mesh screen, while more thanhalf of the granular product was collected on the 20 mesh screen (FIG.6). Particles smaller than 80 mesh (178 μm) made up 4.6% of the product.

Example 7 Three Formulated PVPP Granules for Wine Making

Three granular compositions were made containing PVPP (Polyclar® V,International Specialty Products) with one of two beverage-approvedco-ingredients (Table 4). The granules were compacted using a TF MiniRoller Compactor (Vector Corporation, Marion, Iowa) with a screw speedof 40 rpm, a roller speed of 5 rpm, and a roller pressure of 4 tons. Theresultant ribbons from the roller compaction process were granulatedusing an Erweka® AR400 Oscillating Granulator (Heusenstamm, Germany)fitted with a 10 mesh screen (2 mm). Low-dusting granules were produced.FIGS. 7, 8, and 9 illustrate the granulated products of this Example.

The three granular compositions were size fractionated using fourscreens, 80 mesh (0.178 mm), 40 mesh (0.422 mm), 20 mesh (0.854 mm), and10 mesh (2.06 mm). As in Example 6, the majority of granulated productwas collected on the 20 and 40 mesh screens; no material collected onthe 10 mesh screen, and very little product was collected on the 80 meshscreen (Composition A—FIG. 10, Composition B—FIG. 11). In bothcompositions particles smaller than 80 mesh (178 μm) made up less than3% of the product.

In a comparison of measurement methods, the particle size distributionsof the three granular compositions also were measured using alight-scatter analyzer (LA-950 Particle Size Analyzer, Horiba Ltd.).

TABLE 4 Compositions of formulated PVPP granules sodium bentonite PVPPcellulose fiber (Volclay Composition (Polyclar ® V) (Fibra-Cel ® BH-40)KWK 200) A 30% 15% 55% B 70% 15% 15% C 80% 20% 0%

Example 8 Treatment of White Wine for Total Polyphenol Control

Compositions A-C were used to treat a sauvignon blanc white wine anddetermine the effect of granule composition on total polyphenol content.

First, aqueous slurries of each composition from Example 7 were preparedat 10% (w/v) and hydrated for 24 hours prior to dosing to allow thebentonite component (if present) to gel fully. Samples of the white winewere dosed at room temperature (approximately 22° C.) with each slurryat two dose rates, 25 g/hL and 50 g/hL. Dosed wine samples were given a1-hour contact time with the granules while under continuous agitationvia platform shaker. Afterward, samples were vacuum filtered though aWhatman glass fiber filter. A 5% (w/v) sodium metabisulfite preservativesolution was added to all conditions at an addition level of 1.2 ml/L.The one control (processed without any added unprocessed feedstock orcomposition from Example 7) and three experimental conditions wereplaced on accelerated testing by incubating them for up to 3 weeks at50° C.

Filtered aliquots of untreated and treated samples were analyzed byultraviolet/visible spectroscopy (Cintra® 40, GPC Scientific,) and ahaze meter, LG Automatic Haze Meter, calibrated using turbiditystandards (AMCO Clear Primary Standards, GFS Chemicals). As is standardin the industry, total polyphenol content was the measured absorbance at275 nm, and samples were diluted with deionized water (as needed) inorder to bring the reading within measurable limits, and the reading wasmultiplied by dilution faction to give the polyphenol index.

Compositions A-C provided up to about 1 percentage point reduction (or28% of the initial) in the total polyphenol content of the white wine(FIG. 12). Consumers may notice this reduction as an improvement in theflavor profile, since the wine is less astringent.

Example 9 Treatment of White Wine for “Pinking”

The method described in Example 8 was repeated in order to determine theeffect of compositions A-C (from Example 7) on “pinking” of white wine,being measured as the absorbance at 520 nm.

Compositions A-C achieved a significant reduction in age-related“pinking” of the white wine. At both dose rates, Compositions A-Clessened the natural increase of “pinking” noted in the untreatedcontrol (FIGS. 13A and 13B). The greatest reduction in “pinking” wasattained using the treatment of Example 8 and Example 9 at the higherdose rate of 50 g/hL.

Example 10 Treatment of White Wine for “Browning”

The method described in Example 8 was repeated in order to determine theeffect of compositions A-C (from Example 7) on “browning” of white wine,being measured as the absorbance at 420 nm.

The granulated compositions produced in Example 7 reduced the extent ofsauvignon blanc “browning” over time (FIGS. 14A and 14B). Both doselevels of 25 g/hL and 50 g/hL proved effective, with the greaterreduction in browning at the higher level.

The “pinking” and “browning” data reveal that the compositions of theinvention are useful for treating white wine in order to minimizenatural color changes that occur as wine ages. The color agents removedfrom the white wine also are known by one skilled in the art tocontribute to off-flavors. Indeed, it has been experienced that whitewine thus treated also exhibit an enhanced flavor profile.

Example 11 Treatment of White Wine for Haze Control

The method described in Example 8 was repeated in order to determine theeffect of compositions A-C (from Example 7) on white wine haze, beingmeasured at ambient room temperature (about 22° C.) using an LgAutomatic haze meter calibrated using EBC haze standards.

The development of haze considerably decreased after treating white winewith the granulated compositions A-C (FIGS. 15A and 15B). As noted for“pinking” and “browning,” compositions B and C controlled thedevelopment of haze the best. After 21 days the white wine samples thustreated developed half as much haze as the untreated control.

There is a strong consumer demand for white wines that display little orno haze; clear wines are preferred. Hence, compositions of theinvention, and the use thereof to treat white wine find great utility tohelp wine makers produce a high-value product.

Example 12 Treatment of Red Wine for Total Polyphenol Control

The methods described in Example 8 was repeated to treat a merlot redwine and determine the effect the granulated PVPP compositions on totalpolyphenol content. The sodium metabisulfite preservative solution levelreported in Example 8 was reduced to 0.6 ml/L, and the dose rates alsowere reduced to 15 g/hL and 25 g/hL.

Due in part to the higher level of total polyphenols in red wine thanwhite wine (42 percentage points vs 3.6 percentage points), the blendedPVPP granules of Example 7 attained a larger reduction in totalpolyphenols, up to 8 percentage points (FIG. 16) than was measured forwhite wine. Both the granule formulation and dose rate were influentialin determining the final total polyphenol content of the treated wine.In this experiment, composition C (80% PVPP, 20% cellulose) at 25 g/hLdose rate provided the greatest total polyphenol reduction.

As described in Example 8 for white wine, the reduction in totalpolyphenols may be noticed as an improvement in the flavor profile,since the wine is less astringent.

Example 13 Treatment of Red Wine for Color Control

The method of Example 10 was repeated wine to assess the influence ofPVPP granule formulations on red wine color. Whereas the absorption at420 nm is used to assess the “browning” of white wine, this value isused to describe the color of red wines. In this example the dose rateswere 15 g/hL and 25 g/hL.

As described for white wine, the formulated granules successfullylimited the “color” aging of red wine relative to the untreated control(FIGS. 17A and 17B).

As noted for white wines, there also is a strong consumer demand for redand rose wines that display color brilliance, meaning having a colorpalate that is red or pink in nature and without brown. Hence,compositions of the invention, and the use thereof to treat red and rosewines, find great utility to help wine makers produce a high-valueproduct.

The invention has been described in detail with particular reference topreferred embodiments thereof, but it will be understood that variationsand modifications can be effected within the spirit and scope of theinvention.

1. A granular composition comprising at least 15% (w/w) crosslinkedpolyvinylpyrrolidone (PVPP).
 2. The composition of claim 1 whereinparticles 100 μm and smaller make up 10% (w/w) or less of saidcomposition.
 3. The composition of claim 2 wherein particles 100 μm andsmaller make up 5% (w/w) or less of said composition.
 4. The compositionof claim 3 wherein particles 170 μm and smaller make up 10% (w/w) orless of said composition.
 5. The composition of claim 1 possessing 80%or more of the polyphenol absorptivity compared to ungranulatedfeedstock.
 6. The composition of claim 1 further comprising one or moreingredients selected from the group consisting of: beverage processaides, absorbents, adsorbents, clarifiers, stabilizers, disintegrants,disintegration aides, binders, active ingredients, cleaning ingredients,lubricants, plasticizers, wicking agents, and blends thereof.
 7. Thecomposition of claim 6 wherein said ingredient is used in thepreparation of beverages.
 8. The composition of claim 7 wherein saidingredient is selected from the group consisting of: activated carbons,bentonite clays, carrageenans, diatomaceous earths, cellulose fibers,polysaccharides, silicas, and blends thereof.
 9. The composition ofclaim 8 that essentially comprises: PVPP, cellulose fiber, and sodiumbentonite.
 10. The composition of claim 8 that essentially comprises:PVPP and cellulose fiber.
 11. The composition of claim 1 thatessentially comprises: PVPP.
 12. The composition of claim 6 wherein saidactive is selected from the group consisting of biocides, fertilizers,nutritionals, pharmaceutical actives, and blends thereof.
 13. Thecomposition of claim 12 wherein said biocide is selected from the groupconsisting of algaecides, aquaticides, insecticides, fungicides,germicides, herbicides, larvicides, pesticides, rodentcides,taeniacides, and blends thereof.
 14. The use of a granular compositioncomprising at least about 15% (w/w) crosslinked polyvinylpyrrolidone(PVPP) in the preparation of beverages.
 15. The use of claim 14 whereinsaid preparation involves the removal of polyphenol, protein, or bothpolyphenol and protein.
 16. The use of claim 14 wherein said beverage isan alcoholic beverage or a non-alcoholic beverage.
 17. The use of claim16 wherein said alcoholic beverage comprises: beer or wine.
 18. The useof claim 16 wherein said non-alcoholic beverage comprises: fruit juice,tea, or blends thereof.
 19. The use of a granular composition comprisingat least about 15% (w/w) crosslinked polyvinylpyrrolidone (PVPP) in themanufacture of biocide, agricultural, or cleaning products.
 20. A methodfor producing low-dusting PVPP compositions, said method comprising: (A)compacting a feedstock having at least about 15% (w/w) crosslinkedpolyvinylpyrrolidone, and (B) breaking said feedstock into granules,grains, or particles.